Calcium Separation from Manganese Sulfate Liquid and Preparation of Manganese Carbonate
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摘要:
硫酸锰矿液存在低浓度钙离子难分离的问题，不利于硫酸锰矿液的进一步利用。本研究对比了氟化法和氨化法分离硫酸锰矿液中钙的效果，并详细探究了氟化铵用量、pH值调节剂、碳酸铵沉淀剂用量、反应温度以及pH值对钙分离效果及锰离子损失的影响。实验表明，氟化法分离钙的较佳条件为：使用氨水调节pH值到4.5，氟化铵与锰的用量比为3∶1、碳酸铵与锰的用量为3∶4、反应温度为90 ℃。氨化法分离钙的较佳pH值为9.5。值得注意的是，两种方法不仅能分离低浓度的钙，也能使镁的分离率高于90.0%。对比氟化法，氨化法可使钙的分离率达到83.3%，且能将锰离子损失量降到较低。此外，将氨化法分离钙镁后所得的硫酸锰溶液中的锰离子进行进一步利用，成功制备出了高纯的碳酸锰。
Abstract:The problem of difficult separation of low concentration calcium ions in manganese sulfate ore solution is not conducive to its further utilization. This study compared the effects of fluorination and ammonification methods on the separation of calcium from sulfuric acid manganese ore solution, and investigated in detail the effects of ammonium fluoride dosage, pH value regulator, ammonium carbonate precipitant dosage, reaction temperature, and pH value value on calcium separation efficiency and manganese ion loss. Experiments have shown that the optimal conditions for separating calcium by fluorination are: adjusting the pH value to 4.5 using ammonia water, a ratio of 3:1 between ammonium fluoride and manganese, a ratio of 3:4 between ammonium carbonate and manganese, and a reaction temperature of 90 ℃. The optimal pH value for separating calcium by ammonification method is 9.5. It is worth noting that both methods can not only separate low concentrations of calcium, but also achieve a separation rate of over 90% for magnesium. Compared to the fluorination method, the ammonification method can achieve a calcium separation rate of 83.3% and minimize the loss of manganese ions. In addition, high-purity manganese carbonate was successfully prepared by further utilizing the manganese ions in the manganese sulfate solution obtained by the ammonification method for separating calcium and magnesium.
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表 1 不同氟化铵用量下分别加入氨水与氢氧化钡反应后c(Mn/Ca)
Table 1. C(Mn/Ca) after adding ammonia water and barium hydroxide at different dosages of ammonium fluoride
m(NH4F/Mn) 加氢氧化钡c(Mn/Ca) 加氨水c(Mn/Ca) 1 557 455 2 832 626 3 826 1 051 
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表 2 不同锰初始浓度下各离子沉淀率和c(Mn/Ca)
Table 2. Precipitation efficiencies and c(Mn/Ca) of various ions at different initial manganese concentrations
硫酸锰液稀释倍数 Mn损失率 Ca沉淀率 Mg沉淀率 c(Mn/Ca) 1 7.5% 46.8% 77.0% 644 2 6.0% 27.7% 61.5% 481 5 3.9% 7.8% 39.9% 385
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表 3 不同碳酸铵加入量反应后c(Mn/Ca)
Table 3. C (Mn/Ca) after adding different amounts of ammonium carbonate
m((NH4)2CO3/Mn) 0 0.25 0.5 0.75 1 c(Mn/Ca) 370 474 624 659 690
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表 4 不同反应温度下各离子沉淀率和c(Mn/Ca)
Table 4. Precipitation efficiencies of various ions at different reaction temperatures
反应温度/℃ Mn损失率/% Ca沉淀率/% Mg沉淀率/% c(Mn/Ca) 50 25.6 43.9 96.3 490 70 30.1 73.9 96.6 991 90 25.3 82.5 97.0 1978
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表 5 氨化反应不同pH值下离子沉淀率
Table 5. Ions precipitation efficiencies at different pH value in ammonification reaction
pH值 Mn损失率/% Ca沉淀率/% Mg沉淀率/% 8.9 67.9 14.8 7.0 9.5 87.0 16.7 7.6 10.5 84.2 11.1 20.8
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